Production of organolithium compounds and lithium hydride

ABSTRACT

A catalytic system is provided for the lithiation of α-olefins and α,ω-diolefins with concurrent production of lithium hydride. The catalysts include oxygen and sulfur containing organic compounds and polycyclic aromatics which can be combined with alkali metals and/or transition metal compounds. High yields of pure and stereospecific lithiated olefins are obtainable.

FIELD OF THE INVENTION

The present invention relates to a catalyst system for the preparationof organolithium compounds for lithium and olefins with concurrentproduction of an equimolar amount of lithium hydride.

BACKGROUND OF THE INVENTION INCLUDING PRIOR ART

The conventional technical method of producing organolithium compounds(Kirk-Othmer, "Enc. Chem. Techn.", Vol 12, p. 547, 1967) is based on thereaction of lithium metal with organic halogen compounds, in whichorganolithium compounds as well as lithium halides are produced:

    RX+2 Li→RLi+LiX                                     (1)

X=Cl, Br, I

Allyllithium and benzyllithium compounds may among others be produced bythe splitting of the corresponding ether derivative or acyloxyderivative with lithium metal (J. A. Katzen-ellenbogen R. S. Lenox, J.Org. Chem., 38, 326, 1973; U. Schollkopf in "Methoden der OrganischenChemie", Houben-Weyl, XIII/1, P. 161; J. J. Eisch, A. M. Jacobs, J. Org.Chem. 28, 2145, 1963):

    ROR'+2Li→R-Li+R'OLi                                 (2)

R=allyl, benzyl

R'=phenyl, mesitoyl

From the organolithium compounds so produced, numerous otherorganolithium compounds may be obtained by means of metal-H exchange:

    R-Li+R'H→R-H+R'-Li                                  (3)

or by means of metal-halogen exchange (D. Seebach. K.-H. Geiss in "NewApplications of Organometallic Reagents in Organic Synthesis", p.1,Elsevier, 1976):

    R-Li+R'-X→R'-Li+R-X                                 (4)

X=Cl, Br, I

Only in exceptional cases had it heretofore been possible to synthesizeorganolithium compounds directly from lithium metal and hydrocarbons.Thus, for instance, 1-alkines (H. Ogura, H. Takashi, Synth. Commun., 3135, 1973), triphenylmethane or acenaphtylene (B. J. Wakefield, "TheChemistry of Organolithium Compounds", p. 70, Pergamon Press, 1974) maybe lithiated with metallic lithium. According to D. L. Skinner et al (J.Org. Chem., 32, 105, 1967) lithium reacts with 1-alkenes in the absenceof a solvent to produce 1-alkinyllithium compounds and lithium hydride:

    RCH═CH.sub.2 +4 Li→RC.tbd.C-Li+3 LiH            (5)

whereby 1-lithio-1-alkenes are produced as byproducts of the reaction,at very small yields. In the presence of tetrahydrofuran (THF)1-lithio-1-hexene was obtained from lithium and 1-hexene at boilingtemperatures, at 9% yield.

A procedure for the preparation of organolithium compounds from lithiumand ethylene in dimethoxymethane or THF in the presence of biphenyl and,if the case, naphthalene was recently made known (V. Rautenstrauch ofFirmenich S. A., Geneva, Swiss Pat. No. 585, 760, May 20, 1974; V.Rautenstrauch, Angew, Chem., 87, 254, 1975). The yields of organolithiumcompounds according to these procedures are at very low levels. Sincethe reaction products furthermore occur in the form of a mixture ofvinyllithium and 1,4-dilithiobutane, this procedure hardly seemssuitable for technical purposes.

SUMMARY OF THE INVENTION

The present invention provides a catalyst comprising a composition ofthe formula ##STR1## wherein

A and B are sulfur or oxygen

G is a carbon atom bonded to a radical R¹

D is a carbon atom bonded to a radical R² and there is a double bondbetween the carbon atom of G and of D;

E is carbon

F is oxygen, sulfur, ##STR2##

Me is an alkaline metal

n is an integer from 2 to 20;

L and L' are mono or poly-functional ethers or amines;

p and q are integers from 0 to 4;

R¹, R², R³ and R⁴ are independently hydrogen, alkyl, cycloalkyl, aralkylor aryl groups and/or two or more of such groups are closed into analiphatic or aromatic ring system; and

a metal compound of transition metals from group Ib, IIb, IVb, Vb, VIb,VIIb and VIII of the transition metals of the periodic system.

Preferably R¹, R², R³, R⁴ have less than about 20 carbon atoms. Alkylgroups include methyl, ethyl, isopropyl, n-decyl, stearyl.

Cycloalkyl groups include cyclopentyl, cyclohexyl, decahydronaphthyl.

Aralkyl groups include benzyl, phenylethyl and naphthyl methyl. Arylgroups include phenyl, tolyl, xylyl, naphthyl, penanthryl and diphenyl.

Two groups closed in to an aliphatic ring system include propylene andbutylene groups.

Two groups closed into an aromatic ring system include benzo and naphthogroups.

Preferably the ratio of moles of the composition of the formula (*) tothe moles of transition compound is in the range from about 1:10 to10:1.

In the formulas (*) above, (**) and (***) below, certain single bondinglines may represent double bonds and there can also be a bond between Aand B when both A and B are sulfur.

Preferred catalysts of the present invention includes those wherein thecomposition has the following formula: ##STR3## and wherein

X is sulfur or oxygen.

A more preferred composition has the formula ##STR4## and the metalcompound is cuprous chloride or ferric chloride.

Another preferred catalyst has a composition of the formula ##STR5##wherein

X is sulfur or oxygen.

More preferred are catalysts of the formula (II)

wherein

X is sulfur,

R¹ =R⁴ is C₆ H₅, and

R² =R³ is hydrogen and

Me is lithium and

wherein the metal compound is zinc chloride, or palladium chloride or

wherein

X is sulfur

R¹ =R³ is C₆ H₅,

R² =R⁴ is hydrogen and

Me is lithium, and

wherein the metal compound is cupric chloride.

The metal compound can be of a metal selected from the groups consistingof copper, gold, zinc, cadmium, titanium, zirconium, vanadium, niobium,tantalum, chromium, molybdenum, tungsten, manganese, iron, cobalt,nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum.

Preferred metal compounds are of a metal selected from the groupconsisting of copper, iron, zinc, palladium, platinum and rhodium.

Preferred metal compounds include halides and organic complexes such asacetylacetonates, more preferred are transition metal chlorides.

Exemplary metal compounds include compounds selected from the groupconsisting of

zinc chloride,

iron (III) chloride

copper (I) chloride

copper (II) chloride

molybdenum (VI) chloride

titanium (IV) chloride

chromium (III) chloride

molybdenum (V) chloride

managanese (II) chloride

cobalt (II) chloride

nickel (II) chloride

nickel (II) acetylacetonate

rhodium (III) chloride

platinum (II) chloride

palladium (II) chloride

The metal compound is preferably an anhydrous metal compound.

In one aspect, the present invention provides a catalyst composition ofmetal complexes comprising

a polycyclic aromatic compound;

an alkali metal; and

a metal compound of transition metals from group Ib, IIb, IVb, Vb, VIb,VIIb and VIII of the periodic system.

The polycyclic aromatic compound has preferably from about 10 to 24carbon atom. Typical aromatic compounds include

naphthalene,

anthracene,

phenanthrene, and

diphenyl

P The alkaline metal can be lithium, sodium or potassium and morepreferred is lithium.

The present invention also provides a process for preparation of organolithium compounds and lithium hydride comprising contacting lithium withα olefin or an α,ω-diolefin in the presence of a catalyst comprising:

a metal organic composition of the formula ##STR6## wherein

A and B are sulfur or oxygen,

G is carbon bonded to a radical R₁

D is carbon bonded to a radical R₂, and, if A and B are oxygen, also toa hydrogen atom,

E is carbon,

F is a member of the group consisting of

oxygen,

sulfur,

hydroxy

where

B is oxygen, ##STR7##

R¹, R², R³, RHU 4 represent hydrogen, alkyl, cycloalkyl, aralkyl or arylgroups and/or two or more of such groups are closed into an aliphatic oraromatic ring system, and

M* represents a metal compound of metals from groups Ib, IIb, IVb, Vb,VIb, VIIb, and VIII or the periodic system and/or a group Me_(n) (L)_(p)(L')_(q)

wherein

Me is an alkali metal

n is an integer from 2 to 20;

L and L' are monofunctional or polyfunctional ethers or amines, and

q and q are integers from 0 to 4; and/or a composition of metalcomplexes comprising polycyclic aromatics, an alkali metal, and a metalcompound of transition metals from group Ib, IIb, IVb, Vb, VIb, VIIb andVIII of the periodic system.

If A and B are sulfur in formula (II) there can be a bond between A andB and when ##STR8## there is a bond between B and the sulfur atom of the##STR9##

A preferred metal organic composition employed in the process has theformula ##STR10## wherein X is sulfur or oxygen and more preferred arecatalysts with compositions of the formula ##STR11## and of the formula

The metal organic composition can have the formula ##STR12## wherein

X is sulfur or oxygen, and preferably

wherein

X is sulfur,

R¹ =R⁴ is phenyl,

R² =R³ is hydrogen and

Me is lithium, and

wherein the metal compound is zinc chloride or palladium chloride or

wherein

X is sulfur

R¹ =R³ is phenyl

R² =R⁴ is hydrogen, and

Me is lithium, and

wherein the metal compound is cupric chloride.

The metal compound of the catalyst employed in the process can be themetal compound of a metal selected from the group consisting of copper,gold, zinc, cadmium, titanium, zirconium, vanadium, niobium, tantalum,chromium, molybdenum, tungsten, manganese, iron, cobalt, nickel,ruthenium, rhodium, palladium, osmium iridium and platinum, andpreferably the metal compound is of a metal selected from the groupconsisting of copper, iron, zinc, palladium, platinum and rhodium.

Typical metal compounds include those selected from the group consistingof

zinc chloride,

iron (III) chloride,

copper (I) chloride,

copper (II) chloride,

molybdenum (VI) chloride,

titanium (IV) chloride,

chromium (III) chloride,

molybdenum (V) chloride,

manganese (II) chloride,

cobalt (II) chloride,

nickel (II) chloride,

nickel (II) acetylacetonate,

rhodium (III) chloride,

platinum (II) chloride and

palladium (II) chloride.

Preferably the metal compound is an anhydrous metal compound.

A solvent can be added to the lithium, to the α- or the α,ω-diolefinand/or to the catalyst.

The solvents include cyclic or an open-chain monoether or polyetherssuch as the tetrahydrofuran. The catalyst can be formed in situ, bycontacting lithium with compounds of the general formulae III and IV, orV, VI and VII ##STR13## wherein X is sulfur or oxygen and alternativelylithium is contacted with compounds of the general formulae III, IV, V,VI, or VII and with a metal compound of transition metals from groupsIb, IIb, IVb, Vb, VIb, VIIb, and VIII of the periodic system. Alsolithium can be contacted with a catalyst consisting of isolated adductsbetween compounds III to VII, and metal compounds of transition metalsfrom groups Ib, IIb, IVb, Vb, VIb, VIIb and VIII of the periodic system.

Preferably a member of the group consisting of the reaction products ofthe formulae ##STR14## is contacted with lithium.

In a further aspect of the invention lithium is contacted with acatalyst, produced from a polycyclic aromatic compound such asanthracene, naphthalene or biphenyl and a metal compound of metals fromsubgroups Ib, IIb, IVb, Vb, VIb, VIIb and VIIIb of the periodic system.

The contacting can be from about -100° C. to +100° C., and is preferablyfrom about -20° C. and +50° C. Preferably the partial pressuresprevailing in the process are less than about 100 bar. The α-olefinesinclude those of the general formula CH₂ ═CHR, wherein R is H, alkyl,aryl, cycloalkyl or aralkyl, and the α,ω diolefins include those of theformula CH₂ ═CH--(CHR)_(n) --CH═CH₂ wherein R is hydrogen, alkyl, aryl,cycloalkyl or aralkyl and n is an integer from 1 to 6.

In a further aspect of the invention, a process is provided forpreparation of a catalyst comprising contacting

an organic compound of the formula ##STR15## wherein

A and B are sulfur or oxygen

G is a carbon atom bonded to a radical R₁

D is a carbon atom bonded to a radical R₂ and there is a double bondbetween the carbon atom of G and of D.

E is carbon

F is oxygen sulfur, ##STR16##

R¹, R², R³ and R⁴ are independently hydrogen, alkyl, cycloalkyl, aralkylor aryl groups and/or two or more of such groups are closed into analiphatic or aromatic ring system;

an alkaline metal; and

mono or poly-functional ethers or amines.

A metal compound of transition metals from groups Ib, IIb, IVb, Vb, VIb,VIIb and VIII of the periodic system can be added to the resultingcomposition.

Preferred organic compounds in perparing the catalyst include those ofthe formulas ##STR17## wherein X is sulfur or oxygen.

DETAILED DESCRIPTION OF THE INVENTION INCLUDING PREFERRED EMBODIMENTS

In accordance with the present invention, is was surprisingly found thatα-olefins and α,ω-diolefins can be reacted with metallic lithium in thepresence of appropriate catalysts, and the reaction products includepure and stereospecific organolithium compounds and lithium hydride. Thereaction between lithium and olefins is carried out for practicalreasons in solvent such as a cyclic or open-chain monoether or polyether(preferably tetrahydrofuran, THF) at temperatures from about -100° to+100° C. and preferably from about -20° C. to +50° C. and at partialpressures of preferably below 1 bar and at from about 1 to 100 barpressure.

Accordingly, the invention relates to a process for production oforganolithium compounds in addition to lithium hydride, wherein lithiumis contacted with a catalyst from the following group:

(a) an alkali-metal complex compound of the general formulae I or II##STR18## wherein

Me is an alkali metal;

X is sulfur or oxygen;

n is an integer from 2 to 20;

L and L' are monofunctional or polyfunctional ethers or amines,

p and q are integers from 0 to 4;

R¹, R², R³ and R⁴ are hydrogen, alkyl, cycloalkyl, aralkyl or arylgroups, and/or where two or more of such groups are closed into analiphatic or aromatic ring system; or

(b) a catalyst according to (a) in the presence of a metal compound oftransition metals from group Ib, IIb, IVb, Vb, VIb, VIIb, and VIII ofthe periodic system; or

(c) a catalyst, produced from polycyclic aromatics such as anthracene,naphthalene and biphenyl and alkali metal in the presence of a metalcompound of transition metals from group Ib, IIb, IVb, Vb, VIb, VIIb,and VIII of the periodic system; or

(d) adducts between compounds of the general formulae III to VII##STR19## in which R¹, R², R³ and R⁴ have the meanings indicated under(a), and transition-metal compounds of transition metals from group Ib,IIb, IVb, Vb, VIb, VIIb and VIII of the periodic system in a solventwith an α-olefin or α,ω-diolefin.

The catalysts mentioned above under (a) and their preparation aredescribed in German Patent Disclosure Record No. 27 22 221.5.

The invention furthermore relates to catalysts from

(a) an alkali metal complex compound of the general formulae I or II##STR20## in which Me is an alkali-metal; X is sulfur or oxygen; n is aninteger from 2 to 20; L and L' are monofunctional or polyfunctionalethers or amines; p and q are integers from 0 to 4; R¹, R², R³ and R⁴are hydrogen, alkyl, cycloalkyl, aralkyl or aryl groups and/or where twoor more of such groups are closed into an aliphatic or aromatic ringsystem; and

(b) metal compounds of transition metals from group Ib, IIb, IVb, Vb,VIb, VIIb, and VIIIb of the period system or from

(c) complexes of polycyclic aromatics such as anthracene, naphthaleneand biphenyl, and an alkali-metal with

(d) a metal compound of transition metals of group Ib, IIb, IVb, Vb,VIb, VIIb, and VIII of the periodic system.

Among the metals from the group Ib, IIb, IVb, Vb, VIb, VIIb and VIIIb ofthe periodic system are included copper, gold, zinc, cadmium, titanium,zirconium vanadium, niobium, tantalum, chromium, molybdenum, tungsten,manganese, iron, cobalt, nickel, ruthenium, rhodium, palladium osmium,iridium or platinum. Of these, we prefer copper, iron, zinc, palladium,platinum and rhodium.

Examples for the monofunctional or polyfunctional ethers or aminesdesignated by an L or L', in general formulae I and II, are as follows:Cyclic ethers such as tetrahydrofuran or glycol ether, and amines suchas tetramethylethylene diamine or morpholine. The monofunctional orpolyfunctional ethers or amines have preferably less than about 10carbon atom. Catalyst formation may also be carried out in a manner suchthat compounds of the general formulae III, IV, V, VI, and VII--whichare also described in German Patent Disclosure Record No. 27 22221.5--are mixed with alkali metals, preferably lithium, and, ifappropriate, with a metal compound of metals from subgroups Ib, IIb,IVb, Vb, VIb, VIIb and VIIIb of the periodic system, in an appropriatesolvent; and, if appropriate, in the presence of α-olefins orα,ω-diolefins. A particularly active and selectively operating catalystsystem, in the sense of the present procedure, is produced, if2,5-diphenyl-1,6,6a-trithiapentalene (V, R¹ ═R⁴ ═C₆ H₅, R² ═R³ ═H) isconverted in combination with zinc chloride in the presence ofα-olefines or α,ω-diolefins in THF with lithium (see Examples 40-42).

Finally, it is also possible to let isolatable adducts between compoundsof the general formulae III-VII, listed above under (d), andtrasition-metal compounds of groups Ib, IIb, IVb, Vb, VIIb or VIIIb ofthe periodic system operate as catalysts on the lithium and olefin ordiolefin. Thus, for instance, iron (III) chloride, copper (I) chloride,and copper (II) chloride, as well as molybdenum (V) chloride form, with1,2-dithiol-3-thiones or 1,6,6a-trithiapentalenes, 2:1 adducts which maybe used instead of a mixture of both components to produce thecatalysts. By the same token, the complexortho-chloropalladio-2,5-diphenyl-1,6,6a-trithiapentalene(6) which canbe produced from 2,5-diphenyl-1,6,6a-trithiapentalene and PdCl₂ yieldswith lithium in THF an active catalyst for the lithiation of olefins:##STR21##

The catalytic lithiation of ethylene with the aid of the catalystsaccording to the invention, in for instance THF, lead to vinyllithiumand lithium hydride: ##STR22##

The vinyllithium soluble in THF may be separated from the insolublelithium hydride and may be further used in solution or isolated incrystalline form. Depending on the catalyst, the yields of vinyllithiumrange from 60 to more than 70% of the amount calculated according to(7).

In the catalytic lithiation of propene according to the procedure of theinvention, there are generally produced four isomeric organolithiumcompounds: Trans-1-propenyllithium (9), cis-1-propenyllithium (10),isopropenyllithium (11) and allyllithium (12), in addition to lithiumhydride: ##STR23## The selectivity of this reaction in relation to theformation of individual isomers may be controlled through the selectionof the catalysts. Thus, in the presence of catalysts produced with theuse of iron, copper, cobalt or zinc compounds, trans-1-propenylithium 9is produced at high selectivity. On the other hand, the catalyticlithiation of propene may be controlled by using palladium, platinum orrhodium compounds in a manner such that predominantly allyllithium 12 isproduced. One catalyst that operates in a particularly selective fashionin this sense was found to be the palladium complex (6), with the aid ofwhich allyllithium may be obtained with a selectivity of 85-90%. In theexample of lithiation of 1-butene with this palladium complex as acatalyst it is shown that higher α-olefins may also be selectivelylithiated in the allyl position. On the other hand, using catalystsproduced with the utilization of zinc, iron or copper compounds, higher1 alkenes such as 1-butene, 1-pentene, 1-octene and 1,7-octadiene mayalso be selectively lithiated in the trans-1 position. Thus, forinstance, 1-octene may be lithiated with the aid of above-mentionedcatalyst from 2,5-diphenyl-1,6,6a-trithiapentalene and ZnCl₂, with aselectivity of more than 96% in the 1-trans position. ##STR24##

R=CH₃, C₂ H₅, n--C₃ H₇, n--C₆ H₁₁, --(CH₂)_(n) -etc.

If appropriate, the trans-1-lithio-1-alkenes may be isolated inanalytically pure crystalline form. By means of crystallization, theratio of trans-1-lithio-1-alkene is generally raised. The presentprocedure thus permits a selective preparation of trans-1-alkenyl orallyllithium compounds from α-olefins or diolefins and lithium.

In the catalytic lithiation of 1,4-pentadiene in the presence of the4,5-benzodithiol-3-thione.2CuCl₂ complex there is produced a heretoforeunknown organolithium compound with the following structure: ##STR25##

The starting point materials for the preparation of organolithiumcompounds in accordance with the present invention are preferablyα-olefins and α,ωolefins having up to about 40 carbon atoms. Theyinclude those of the general formulae CH₂ ═CHR, in which R═H, alkyl,aryl, cycloalkyl or aralkyl; or diolefins of the general formulae CH₂═CH--(CHR)_(n) --CH═CH₂, in which R has the same significance as above,and n=1-6.

The catalytic lithiation of α-olefins or α,ω-diolefins in accordancewith the invention represents a new method of preparation oforganolithium compounds which cannot be produced in any other way or canonly be produced with great difficulty. In lieu of the expensive andoften toxic as well as hard-to-procure organohalogen compounds, thepresent procedure uses commercially available olefins. Moreover, whenthe conventional method is used, one-half of the lithium that is usedwinds up as a lithium halide, and is thus lost for further conversion.The procedure according to the invention supplies, besides theorganolithium compound, highly reactive and technically valuable lithiumhydride. The entire amount of lithium applied is converted into valuablelithium compounds.

The present procedure permits a regioselective or stereoselectivesynthesis of organolithium compounds, providing the capability ofcontrolling the reaction by the proper choice of the catalyst or thereaction conditions, in a manner such that, depending on the need,different organolithium compounds may be obtained from the samestarting-point olefin.

The organolithium compounds that can be prepared by the presentprocedure may be used as initiators for anionic polymerisations ofmono-olefins or diolefins, or as reagents for the introduction oforganic unsaturated groups, as well as for reduction in organicsynthesis.

The following examples represent preferred embodiments of the presentinvention.

EXAMPLES

All experiments for the preparation of organolithium compounds arecarried out in a protective gas atmosphere, such as argon.

EXAMPLE 1 ##STR26## For the preparation of the4,5-benzo-1,2-dithiol-3-thione.2CuCl₂ --complex (13), 2.83 g (21.05mMoles) of anhydrous copper(II) chloride are suspended in 100 ml ofbenzene, are added to 2.00 g (10.85 mMoles) of4,5-benzo-1,2-dithiol-3-thione, and the mixture is stirred for 18 hoursat room temperature. The suspension is filtered, the precipitate iswashed with benzene and dried at 10⁻³ Torr. This yields 3.58 g (75% oftheoretical) of the complex 13.C₇ H₄ S₃ Cu₂ Cl₄ (453.16);

calc. C 18.55, H 0.89, S 21.22, Cu 28.04, Cl 31.29; found C 17.50, H1.00, S 20.90, Cu 27.60, Cl 32.70.

A solution of 1.40 g (3.09 mMoles) of complex 13 in 100 ml of absoluteTHF is saturated with propene (1 bar) at 0° C.; immediately thereafter,5.07 g (0.73 Moles) of lithium sand is added to the solution in apropene atmosphere at 0° C. and under stirring (molar ratio13:Li=1:236). After a temporary temperature rise, the absorption ofpropene starts after 10-15 minutes; the rate of propene absorption canbe measured with the aid of a gas burette connected to the reactionvessel. During the propene absorption, the suspension is stirred, withpropene pressure kept at 1.1-1.2 bar and temperature kept at 0° C. to+2° C. The dark brown reaction mixture absorbs 6.0 liters of propene (1bar, 20° C.) until it is saturated within 49 hours (68.5% oftheoretical). The suspension is filtered at 0° C., the precipitate iswashed with THF and dried at 0.2 Torr. This yields 4.41 g of lithiumhydride mixed with a little lithium (0.135 g of the mixture yield withD₂ O 257 ml of gas (1 bar, 20° C.), consisting of HD (70%), D₂ (19%) andH₂ (11%). For the purpose of analyzing the organolithium compound in thesolution, an aliquot of the solution (8.0 ml of a total of 142.0 ml) isconcentrated under vacuum (0.2 torr) and the solid residue ishydrolyzed. The amount of gas produced thereby is 335.5 ml (1 bar, 20°C.) and consists of propene (84.9%), THF (4.6%), H₂ (3.5%) and acetylene(1.4%). From the amount of propene, Equ. 8 permits calculation of ayield in organolithium compounds LiC₃ H₅ of 57.7%. In order to determinethe distribution of isomers, 58.0 ml of the solution are concentratedunder vacuum (0.2 torr), the residue is dissolved in 60 ml of ether,mixed at 0° C. with 18.9 g (174 mMoles) of trimethylchlorosilane, andthe mixture is stirred 12 hours at 20° C. Hydrolysis or processing anddistillation produces, in addition to hexamethyldisiloxane, 7.3 g of amixture of the isomeric silanes (CH₃)₃ SiC₃ H₅ (B.P. 87°-89° C./760torr), consisting of trans-1-propenyltrimethylsilane 74.5%,cis-1-propenyltrimethylsilane 1.7%, isopropenyltrimethylsilane 8.1%, andallyltrimethylsilane 15.3%.

In order to isolate the trans-1-propenyllithium (9), 74.0 ml of thesolution are concentrated under vaccuum (0.2 torr) to 33.0 ml, added to50 ml pentane, mixed for 10 minutes and filtered. For the purpose ofcrystalizing (9) the filtrate is kept for 3 hours at -40° C. and for 12hours at -78° C. The crystals of (9) are filtered at -78° C., are washedthree times with 40 ml of cold pentane each, dried for one-half hour at-30° C., one-half hour at 0° C. and one hour at 20° C. under vacuum (0.2torr). This yields 9.25 g of the trans-1-propenyllithiumtetrahydrofuranadduct, in the form of light brown crystals (Li-content 6.51; yields45.6% of theoretical, referred to lithium). The ¹ H-NMR spectrum of theproduct ##STR27## (80 MHz, 10% in (C₂ D₅)₂ O; τ=3.39 d (H.sup. 1 ); 3.78m (H 2 ); 6.17 m (H.sup. 4 ), 8.10 m (H.sup. 5 ), 8.18 d (H.sup. 3 );J₁₂ =21 Hz) agrees with that of D. Seyferth and L. G. Vaughan (J.Organomet. Chem. 1, 201, 1963) prepared from trans-1-chloro-1-propeneand lithium (9).

For further purification, 9.0 g of the raw material are recrystalizedfrom a mixture of 18 ml of THF and 32 ml of pentane, as described above.This yields 6.5 g trans-1-propenyllithiumtetrahydrofuran adduct, in theform of colorless crystals. C₃ H₅ Li.C₄ H₈ O (M.W.=120.0); calc. 5.78%Li; found 5.75 Li. The conversion of 6.0 g (49.7 mMole) of this productwith trimethylchlorosilane, as described above, yields 5.43 g of (CH₃)₃SiC₃ H₅ with the following composition: trans-1-propenyltrimethylsilane,93.4%; cis-1-propenyltrimethylsilane, 0.4%; isopropenyltrimethylsilane,1.3%; and allyltrimethylsilane, 4.9%.

EXAMPLE 2 ##STR28##

A solution of 0.90 g (4.9 mMole) of 4.5-benzo-1,2-dithiol-3-thione (BDT)(3a) and 1.63 g (9.8 mMole) of FeCl₃ in 100 ml of THF are saturated withpropene (1 bar) at 0° C.; immediately afterwards 4.87 g (0.70 Moles) oflithium sand are added to the solution in propene atmosphere at 0° C.and with mixing (molar ratio 3a:FeCl₃ :Li=1:2:143). After a temporarytemperature rise, the propene absorption starts after 10-15 minutes.During the propene absorption, the suspension is stirred, the propenepressure is kept at 1.1-1.2 bar and the temperature is kept at 0° C. to+2° C. The reaction mixture absorbs until saturation within 71 hours,3.8 liters of propene (1 bar, 20° C.). The suspension is filtered andthe lithium hydride is washed with THF. Of the total of 114.0 ml of thefiltrates, 8.0 ml are hydrolyzed as described in example 1 whereby 351ml of gas (1 bar, 20° C.) with the composition propene, 75.7%; THF,7.8%; H₂, 8.7%. and acetylene 2.7% are released. From the amount ofpropene, a total yield of LiC₃ H₅ of 45% is calculated according to Equ.8. In the silylation of an aliquot of filtrate, as described in example1, one obtains a mixture of isomeric silanes (CH₃ )₃ SiC₃ H₅, of thefollowing composition: trans-1-propenyltrimethylsilane, 83.8%;cis-1-propenyltrimethylsilane, 1.3%; isopropenyltrimethylsilane, 10.3%;and allyltrimethylsilane, 4.6%. This result means that in the presentcase the catalytic lithiation of propene occurs with a selectivity of83.3% in the trans-1-position of the propene.

EXAMPLES 3 to 12

For the preparation of the 2,4-diphenyl-1,6,6a-trithiapentalene.2CuCl₂--complex (15) Example 6, 3.09 g (23.0 mMoles) of anhydrouscopper(II)chloride are suspended in 100 ml of toluene, added to##STR29## 3.73 g (12.0 mMoles) of2,4-diphenyl-1,1,6,6a-trithiapentalene, and the mixture is stirred for18 hours at room temperature. The suspension is filtered, theprecipitate is washed with toluene, and dried at 10⁻³ torr. One obtains4.0 g (60% of theoretical) of the complex (15). C₁₇ H₁₂ S₃ Cu₂ Cl₄(580.8). calc. C 35.12, H 2.07, S 16.56, Cu 21.88, Cl 24.41. Found C34.85, H 2.55, S 16.34, Cu 21.78, Cl 24.35.

Implementation of the examples 3 to 12 (Table 1): the components of thecatalysts are previously added to THF, the suspension is stirred ifappropriate for 12 hours at 20° C.; immediately thereafter, thepreparations are saturated at respective reaction temperature withpropene (1 bar), and lithium sand is added in a propane atmosphere understirring. The amounts of propene absorbed after specific reaction times(in liters, at 1 bar, 20° C.), as well as the yields of LiC₃ H₅ and theisomer ratios (9:10:11:12) are indicated in Table 1. The determinationof the yields and the isomer ratios are carried out as described inExample 1.

                                      TABLE 1                                     __________________________________________________________________________    Catalytic Reaction of Lithium with C.sub.3 H.sub.6 to LiC.sub.3 H.sub.5       and LiH                                                                                                     Rct.                                                                              Rct. Propene                                                                             LiC.sub.3 H.sub.5                                                                  Composition of                                                                LiC.sub.3 H.sub.5           Example                                                                            Catalyst        THF                                                                              LiSand                                                                              Temp                                                                              Time Absorption                                                                          Yield                                                                              %                           No.  g (mMoles)      (ml)                                                                             g (Mole)                                                                            (°C.)                                                                      (Hrs)                                                                              (liters)                                                                            [%]  (9)                                                                              (10)                                                                             (11)                                                                             (12).sup.(a)       __________________________________________________________________________          ##STR30##      70 1.90(0.27)                                                                          0   74   2.54  75   62.4                                                                             1.8                                                                              14.9                                                                             20.9               4                                                                                   ##STR31##      50 1.30(0.19)                                                                          -20 48   1.08  31   76.6                                                                             1.1                                                                              12.6                                                                             9.7                5                                                                                   ##STR32##      70 1.60(0.23)                                                                          0   52   2.31  78   52.1                                                                             1.0                                                                              9.0                                                                              37.2               6                                                                                   ##STR33##      50 1.06(0.15)                                                                          +20 48   0.79  43   58.2                                                                             1.1                                                                              0.4                                                                              40.2               7                                                                                   ##STR34##      50 1.42(0.20)                                                                          0   42   1.22  45   78.0                                                                             1.9                                                                              13.0                                                                             7.0                8                                                                                   ##STR35##      150                                                                              4.80(0.69)                                                                          0   120  .sup.(d)                                                                            41   79.2                                                                             1.6                                                                              8.9                                                                              10.3               9                                                                                   ##STR36##      100                                                                              5.67(0.82)                                                                          0   67   2.58.sup.(d)                                                                        38                               10                                                                                  ##STR37##      70 1.70(0.24)                                                                          0   48   1.71  47   82.3                                                                             1.9                                                                              9.4                                                                              6.5                11                                                                                  ##STR38##      100                                                                              3.96(0.57)                                                                          0   120  2.73.sup.(d)                                                                        26   82.5                                                                             1.7                                                                              9.7                                                                              6.2                12                                                                                  ##STR39##      100                                                                              5.27(0.76)                                                                          0   98   2.78.sup.(d)                                                                        22   85.5                                                                             2.0                                                                              10.2                                                                             2.3                __________________________________________________________________________     ##STR40##                                                                     .sup.(b) Before addition of Li, the sample was stirred for 12 hours at        20° C.                                                                 .sup.(c) The respective aromatic compound and metal salt were previously      added to THF, the solution was saturated with C.sub.3 H.sub.6, and Li was     added.                                                                        .sup.(d) A propene pressure of 1.1-1.2 bar was used.                     

EXAMPLES 13 TO 24 Implementation of Examples 13 to 24 (Table 2):

4,5-Benzo-1,2-dithiol-3-thione (BDT) (3a) and respective metal salt(molar ratio BDT:metal salt=1:2) are stirred in 60 ml of THF for 12hours at 20° C.; immediately afterwards, the preparation is saturated at0° C. with propane (1 bar), and lithium sand is added in a propeneatmosphere and under stirring. The amounts of propene absorbed afterspecific reaction times (in liters, at 1 bar, 20° C.), as well as theyields of LiC₃ H₅ and the isomer ratios (9:10:11:12) are indicated inTable 2. The determination of the yields and the isiomer ratios arecarried out as described in Example 1.

EXAMPLES 25 TO 27 Preparation of theortho-chloropalladio-2,5-diphenyl-1,6,6a-trithiapentalene complex (8)(Example 25):

To the suspension of 3.10 g (9.94 mMole) of2,5-diphenyl-1,6,6a-trithiapentalene in a mixture of 230 ml of methanoland 25 ml of benzene, one adds 1.76 g (9.92 mMoles) of PdCl₂ followed by1.33 g (31.3 mMoles) of LiCl dissolved in 20 ml methanol. The suspensionis boiled for 3 hours under stirring, with reflux, and after cooling toroom temperature it is filtered through a G-3 glass filter crucible. Inthe mother liquor, 93.6% of the split-off HCl was determinedacidimetrically. The precipitate was washed with methanol and ether andwas dried at 10⁻³ torr. The yield of (8) (M.P. 304° C., decomp.) amountsto 4.38 g (97%). C₁₇ H₁₁ S₃ PdCl (453.8);

Calc. C 44.94, H 2.64, S 21.15, Pd 23.44, Cl 7.82; Fd. C 44.92, H 2.90,S 21.08, Pd 23.21, Cl 7.86.

Implementation of Examples 25 to 27 (Table 3):

                                      TABLE 2                                     __________________________________________________________________________    Catalytic Reaction of Lithium with C.sub.3 H.sub.6 to LiC.sub.3 H.sub.5       and LiH                                                                        ##STR41##                                                                                           Rct.                                                                             Propene                                                                             LiC.sub.3 H.sub.5                                                                  Composition of LiC.sub.3 H.sub.5         Example                                                                            Catalyst     LiSand                                                                             Time                                                                             Absorption                                                                          Yield                                                                              (9)                                                                             (10)                                                                              (11)                                                                             (12).sup.(a)                    No.  g (mMoles)   g (Mole)                                                                           (hrs)                                                                            (liters)                                                                            (%)  [%]                                      __________________________________________________________________________    13   BDT + 2TiCl.sub.4                                                                          1.14(0.16)                                                                         46 1.00  29   84.8                                                                             2.0                                                                              6.5                                                                              6.7                                  0.33(1.8)0.68(3.6)                                                       14   BDT + 2CrCl.sub.3                                                                          1.20(0.17)                                                                         46 1.10  42   83.1                                                                             1.9                                                                              5.5                                                                              9.4                                  0.31(1.7)0.56(3.5)                                                       15   BDT + 2MoCl.sub.5                                                                          1.08(0.16)                                                                         53 0.78  31   68.0                                                                             1.6                                                                              20.0                                                                             10.4                                 0.33(1.8)0.99(3.6)                                                       16   BDT + 2MnCl.sub.2                                                                          1.33(0.19)                                                                         45 1.38  37   75.7                                                                             2.4                                                                              7.0                                                                              15.0                                 0.44(2.4)0.60(4.8)                                                       17   BDT + 2CoCl.sub.2                                                                          1.07(0.15)                                                                         29 1.33  52   80.7                                                                             2.0                                                                              8.2                                                                              9.1                                  0.37(2.0)0.53(4.1)                                                       18   BDT + 2NiCl.sub.2                                                                          1.30(0.19)                                                                         72 1.22  40   64.8                                                                             1.7                                                                              2.4                                                                              31.1                                 0.32(1.7)0.44(3.4)                                                       19   BDT + 2Niacae.sub.2.sup.(b)                                                                0.99(0.14)                                                                         30 0.63       67.0                                                                             2.3                                                                              2.3                                                                              28.4                                 0.29(1.6)0.80(3.2)                                                       20   BDT + 2ZnCl.sub.2                                                                          1.68(0.24)                                                                         48 1.60  53   83.1                                                                             1.0                                                                              9.9                                                                              6.0                                  0.41(2.2)0.61(4.5)                                                       21   BDT + 2RhCl.sub.3                                                                          0.76(0.11)                                                                         48 0.43  39   20.9                                                                             1.2                                                                              6.7                                                                              71.2                                 0.22(1.2)0.49(2.3)                                                       22   BDT + 2PtCl.sub.2                                                                          1.05(0.15)                                                                         48 1.00  51   28.0                                                                             0.3                                                                              3.4                                                                              68.2                                 0.27(1.5)0.77(2.9)                                                       23                                                                                  ##STR42##   0.88(0.13)                                                                         29 1.01  66   39.6                                                                             0.6                                                                              5.9                                                                              53.8                                 0.29(0.9)0.49(1.8)                                                       24   BDT + 2PdCl.sub.2                                                                          1.10(0.16)                                                                         72 1.00  54   55.8                                                                             1.0                                                                              7.6                                                                              35.6                                 0.30(1.6)0.57(3.2)                                                       __________________________________________________________________________     ##STR43##                                                                     .sup.(b) Niacae.sub.2 = Nickel acetylacetonate                           

The solution or suspension of the catalyst in THF is saturated at 0° C.with propene (1 bar) and immediately thereafter lithium sand is added ina propene atmosphere and under stirring. The amounts of propene absorbedat the specific times (in liters, at 1 bar, 20° C.), as well as theyields of LiC₃ H₅ and the isomer ratios (9:10:11:12) are indicated inTable 3. The determination of the yields and of the isomer ratios wascarried out as described in Example 1.

                                      TABLE 3                                     __________________________________________________________________________    Catalytic Reaction of Lithium with Propene to LiC.sub.3 H.sub.5 and LiH       (at 0° C.)                                                                                           Rct.                                                                             Propene                                                                             LiC.sub.3 H.sub.5                                                                 Composition of LiC.sub.3                                                      H.sub.5                            Example                                                                            Catalyst       Solvent                                                                            LiSand                                                                             Time                                                                             Absorption                                                                          Yield                                                                             (9)                                                                              (10)                                                                             (11)                                                                             (12).sup.(a)              No.  g (mMoles)     (ml) g (Mole)                                                                           (hrs)                                                                            (liters)                                                                            (%) [%]                                __________________________________________________________________________    25                                                                                  ##STR44##     THF (50)                                                                           2.45(0.35)                                                                         95 2.58  59  10.2                                                                             0.2                                                                               0.6                                                                             89.1                           1.69(3.7)                                                                26   BDT.sup.(b)    THF  5.09(0.73)                                                                              2.48.sup.(c)                                                                      22  77.4                                                                             1.7                                                                              13.0                                                                              8.0                           0.58(3.2)      (100)                                                     27                                                                                  ##STR45##      THF (50)                                                                          1.53(0.22)                                                                            1.30  36                                          1.89(7.2)                                                                __________________________________________________________________________     ##STR46##                                                                    - -                                                                            ##STR47##                                                                    - -                                                                            ##STR48##                                                                    - -                                                                            ##STR49##                                                                     .sup.(b) BDT = 4,5Benzo-1,2-dithiol-3-thione                                  .sup.(c) A propene pressure of 1.1-1.2 bar was used.                     

EXAMPLES 28 TO 33 ##STR50## Preparation of4,5-benzo-1,2-dithiol-3-thione.2 FeCl₃ -complex (16) (Example 29):

To the suspension of 1.89 g (11.6 mMoles) of the anhydrous FeCl₃ in 80ml of benzene, the solution of 1.07 g (5.8 mMoles) of4,5-benzo-1,2-dithiol-3-thione (3a) in 70 ml of benzene is added indropwise fashion with stirring; immediately thereafter, the mixture isstirred for 24 hours at 20° C. The suspension is filtered, theprecipitate is washed with benzene and dried at 10⁻³ torr. One obtains2.36 g (80% of theoretical) of the complex (16). C₇ H₄ S₃ Fe₂ Cl₆(508.7);

calc. C: 16.52, H: 0.78, Fe 21.97, S 18.90, Cl: 41.84; fd. C: 16.55, H:082, Fe 21.91, S: 18.84, Cl 41.76.

Implementation of Examples 28 to 33 (Table 4):

The catalysts are previously added to THF, the solution is saturatedwith ethylene (1 bar) at 0° C.; immediately thereafter, lithium sand isadded at 0° C. under stirring, in an ethylene atmosphere. The amounts ofethylene absorbed after specific reaction times (in liters, 1 bar and20° C.) are indicated in Table 4. The suspensions were filtered and thelithium hydride was washed with THF. In order to determine the yield ofvinyllithium in the filtrate, aliquots of the filtrate were concentratedunder vacuum and the residues were hydrolyzed. From the amounts ofethylene developed and on the basis of equ. 7, the yields ofvinyllithium indicated in Table 4 were calculated.

In order to isolate the vinyllithium, in Example 28, 85 ml of a total of90 ml of the filtrate were concentrated under vacuum (0.2 torr), theresidue was stirred with 50 ml of pentane for 30 minutes, the suspensionwas filtered and the solid was washed four times with 10 ml of pentaneeach. Upon cooling the filtrate to -40° C., thevinyllithium-tetrahydrofuran adduct crystalized (2.72 g) in the form ofcolorless crystals. C₆ H₁₁ OLi (106.1);

calc. 6.60% Li; fd. 6.60% Li.

In order to determine the lithium hydride, in Example 32, the lithiumhydride obtained upon filtration was dried at 0.2 torr, yielding 4.1 gof a gray powder with 46.7% Li. Of this powder, 0.158 g yielded uponhydrolysis the following: HD 75.0%; D₂ 6.3%; H₂ 6.3%; C₂ H₃ D 2.1%; andTHF 1.3%. From the amount of HD, a yield of LiH of 69% was calculatedaccording to Equ. 7.

                                      TABLE 4                                     __________________________________________________________________________    Catalytic Reaction of Lithium with Ethylene to Vinyllithium                   and Lithium hydride (at 0° C.)                                                                         Rct.                                                                             Ethylene                                                                            LiC.sub.2 H.sub.3 --                 Example                                                                            Catalyst      Solvent LiSand                                                                             Time                                                                             Absorption                                                                          Yield                                No.  g (mMoles)    (ml)    g (Mole)                                                                           (hrs)                                                                            (liters)                                                                            (%)                                  __________________________________________________________________________    28                                                                                  ##STR51##    THF (70)                                                                              1.70(0.24)                                                                         44 2.42  60                                   29                                                                                  ##STR52##    THF (50)                                                                              0.55(0.08)                                                                         24 0.68  72                                   30                                                                                  ##STR53##    THF (50)                                                                              0.82(0.12)                                                                         70 0.93  64                                   31                                                                                  ##STR54##    THF (50)                                                                              1.91(0.28)                                                                         143                                                                              2.03.sup.(b)                                                                        35                                   32                                                                                  ##STR55##    THF (100)                                                                             3.62(0.52)                                                                         130                                                                              5.00.sup.(b)                                                                        44                                   33                                                                                  ##STR56##    1,2-dimethoxy- ethane (100)                                                           1.94(0.28)                                                                         67 0.83.sup.(b)                               __________________________________________________________________________     .sup.(a) Before the addition of Li, the sample was stirred for 12 hours a     20° C.                                                                 .sup.(b) An ethylene pressure of 1.1--1.3 bar was used.                  

EXAMPLE 34

In 100 ml of absolute THF, the following are consecutively dissolved:0.78 g (4.2 mMoles) of 4,5-benzo-1,2-dithiol-3-thione (3a); 1.38 g (8.5mMoles) of anhydrous FeCl₃ ; and, at 0° C., 24.2 g (0.43 Moles) of1-butene; immediately thereafter, the solution was mixed at 0° C. andunder stirring, with 7.30 g (1.05 Mole) of lithium sand. The reactionmixture was stirred a total of 7 days at 0° C. During this period,5.0-ml samples of the solution were withdrawn, filtered, and theirlithium content was determined acidimetrically. After 17 and 70 hours ofreaction time, the samples were found to contain 6.75 and 10.6 g-atomsof lithium, corresponding to a lithium conversion to lithium butenyl andlithium hydride, according to Equ. 9, of 26 and 40%. After 7 days ofreaction time, the reaction mixture was separated by filtration from thelithium hydride and the unconverted lithium, and the precipitate waswashed with THF. A 4.5-ml sample of the filtrate (of a total of 138 ml)yielded upon hydrolysis 218 ml of gas (at 20° C., 1 bar), with 62.5%vol. of butene-1. From this, a yield of LiC₄ H₇ of 40% was calculatedaccording to Equ. 9.

In order to characterize the lithium butenyl, the remaining amount wasmixed with an excess of trimethylchlorosilane in ether, as described inExample 1. This yields 26.2 g of a mixture of the four isomericcompounds (CH₃)₃ SiC₄ H₇ (B.P. 95°-109° C./760 torr), of which the maincomponent is represented at 87.9%, according to the gas chromatogram.According to the ¹ H-NMR-spectrum, ##STR57## (100 MHz, 15% in C₆ H₆,τ=3.89 m (H.sup. 1 ), 4.34d (H.sup. 2 ), 7.98 m (H.sup. 4 ), 9.08t(H.sup. 5 ) and 9.91s (H.sup. 6 ); I₁₂ =18.5 Hz)

the major component is trans-1-trimethylsilyl-1-butene (17), which meansthat the lithiation occurs with a selectivity of 87.9% in the 1-transposition of 1-butene.

EXAMPLE 35

In a manner analogous to that of Example 34, 41.4 g (0.74 Mole) of1-butene are allowed to react in the presence of 2.15 g (4.75 mMoles) ofcomplex (13) (Example 1) as catalyst, with 5.60 g (0.81 Mole) of lithiumsand in 150 ml of THF for 10 days at 0° C. The mixture is filtered andthe solid (LiH+Li) is washed with THF. Of the filtrate (totalling 186ml), 5.0 ml yield, after evaporation of the THF and subsequenthydrolysis, 191 ml of gas (at 20° C., 1 bar), with 80% 1-butene(balance: THF, H₂ and C₂ H₂). On that basis, and following Equ. 9, onecalculates a yield of LiC₄ H₇ of 58% (referred to Li). In order toisolate the trans-1-lithio-1-butene, 110 ml of THF is distilled off fromthe remaining filtrate under vacuum (0.2 torr), 100 ml of pentane areadded, and the mixture is filtered [free of] catalyst remnants at 0° C.Upon letting the filtrate stand at -78° C. overnight, further remnantsof the catalyst are separated. The supernatant solution is fullyevaporated under vacuum (0.2 torr), the residue is dried for severalhours at 10⁻³ torr, taken up in 120 ml of pentane, stirred for a shorttime and filtered. The white frit residue is washed with pentane anddried under 0.2 torr. One obtains 7.8 g of trans-1-lithium-1-butene,containing 9.48% Li. After the silylation of this product withtrimethylchlorosilane, processing and distillation, as described inExample 1, this yields trans-1-trimethylsilyl-1-butene at 97% (accordingto GC analysis), which was identified by ¹ H-NMR-spectroscopy.

EXAMPLE 36

In a suspension of 0.58 g (1.28 mMoles) of 8 (see Examples 25 to 27) in20 ml of THF, 1.81 liters (76 mMoles) of gaseous 1-butene are dissolved,which is followed by mixing the suspension at 0° C. under stirring with0.92 g (0.13 Mole) of lithium sand. After stirring for 50 hours at 0° C.it is filtered and the lithium hydride is washed with THF. An aliquot ofthe solution (4.0 ml of a total of 43.6 ml) yields after evaporation ofthe THF and hydrolysis, 200 ml of gas (at 20° C., 1 bar) with a total of30.0% butenes. On the basis of the amount of butene one calculates ayield of LiC₄ H₇ of 40.7%. Upon mixing an aliquot of the solution withtrimethylchlorosilane, as described in Example 1, one obtains a mixtureof the isomeric silanes (H₃ C)₃ SiC₄ H₇, which are, according to the ¹H-NMR-spectrum or GC analysis, predominantly a mixture of cis- andtrans-1-trimethylsilyl-2-butene.

EXAMPLE 37

To a suspension of 6.29 g (0.91 Mole) of lithium sand in 100 ml of THFare added at 0° C. and under stirring, in consecutive order, 33.8 g(0.48 Mole) of 1-pentene and 1.45 g (2.85 mMole) of complex 16 (Examples28 to 33). The mixture is stirred for 5 days at 0° C., followed byfiltration and washing of the solid (LiH) with THF. Of the total of 169ml of filtrate, 2.50 ml contain, according to the acidimetric lithiumdetermination, 4.30 g-atoms of Li, which corresponds to a yield in LiC₅H₉ of 64%.

In order to characterize the organolithium compound LiC₅ H₉, 86.5 ml ofthe filtrate are mixed with excess trimethylchlorosilane, as describedin Example 1. Processing or distillation yields, among others, 10.6 g ofa fraction (B.P. 133° C./760 torr), which istrans-1-trimethylsilyl-1-pentene (18), according to the ¹H-NMR-spectrum. ##STR58## (80 MHz, 15% in CDCl₃ ; τ3=0.96 m (H.sup. 1 ),4.39 d (H.sup. 2 ), 7.90 m (H.sup. 3 ), 8.57 m (H.sup. 4 ), 9.09 t(H.sup. 5 ), 9.94 s (H.sup. 6 ), J₁₂ =18.5 Hz).

In order to isolate the trans-1-lithio-1-pentene, 80 ml of the filtrateare concentrated under vacuum to 20 ml, are mixed with 80 ml of pentaneand filtered. The filtrate is kept for 12 hours at -78° C., and is thensyphoned off at -78° C. from the catalyst remnants that separated. Thesolution so obtained is completely evaporated under vacuum, the residueis dried at 20° C. and 10⁻³ torr to constant weight, is taken up in 100ml pentane, stirred for one-half hour and filtered. The whiteprecipitate is washed with pentane and dried at 0.2 torr. One obtains3.14 g of trans-1-lithio-1-pentene in the form of white powder. LiC₅ H₉(MW=75.9); calc. 9.32% Li; fd. 9.29% Li.

EXAMPLE 38

In a manner analogous to Example 34, 21.6 g (0.20 Mole) of 1,7-octadieneare left to react in the presence of 1.25 g (2.76 mMoles) of complex 13(Example 1) as catalyst, with 5.82 g (0.84 Mole) of lithium sand in 150ml of THF for 11 days at 0° C. The suspension is filtered and lithiumhydride is washed with THF. Of a total of 172 ml of the filtrate, 5.0 mlcontain, according to the acidimetric determination, 6.94 g-atoms oflithium, corresponding to a total yield of organolithium compounds of57%.

The organolithium compounds in solution are characterized in the form oftheir trimethylsilyl derivatives. For that purpose, 77 ml (of a total of172 ml) of the solution, are mixed with trimethylchlorosilane, asdescribed in Example 1. The processing or distillation yields 7.67 g ofa fraction with B.P. 55°-63° C./0.7 torr, as well as 1.55 g of afraction of B.P. 54°-55° C./10⁻³ torr. According to the ¹H-NMR-spectrum, the first fraction consists oftrans-1-trimethylsilyl-1,7-octadiene (19), and the second fractionessentially of bis-1,8-(trans-trimethylsilyl)-1,7-octadiene (20), i.e.,##STR59## in the case of 1,7-octadiene, the lithiation also occurs withhigh selectivity in the trans-1 position.

EXAMPLE 39

In 150 ml of absolute THF there are suspended or dissolved consecutively1.79 g (3.95 mMoles) of complex 13 (Example 1), as well as 13.0 g (0.19Moles) of 1,4-pentadiene; immediately thereafter one adds to thesuspension, at 0° C. under stirring, 11.1 g (1.60 Mole) of lithium sand.The reaction mixture is stirred for 74 hours at 0° C. After this timeperiod, a 5.0-ml sample of the solution contains 9.42 mg atoms oflithium. The suspension is diluted with 50 ml of THF, filtered at 0° C.and the LiH is washed with THF. During the 48-hour standing of thesolution at -78° C., the organolithium compound 14 crystalizes out inthe form of brown-color, coarse crystal. The crystals are separated fromthe mother liquor at -78° C., are washed with a little THF cooled to-78° C. and dried for one-half hour at 0° C. and one-half hour at 20° C.under vacuum (0.2 torr). One obtains 11.1 g of product with a ratio of9.61% lithium (calc. for C₄ H₅ Li₃ (THF)₂ 9.0% Li). On the basis of the¹ H-NMR or ¹³ C-NMR-spectra in combination with spin-spin-decouplingexperiments, as well as on the basis of the silylation (see below), theorganolithium compound is assigned structure 14. In order to record the¹ H-NMR-spectrum, the product, with 9.61% Li, is recrystalized twicefrom an 1:1 THF-tetramethylethylenediamine mixture (crystalizationrespectively at -78° C.). The ¹ H-NMR-spectrum of 14 (15% in d₈ -THF;270 MHz; 27° C.; d-THF as internal standard): δ=7.54 dd (H¹), 5,37 d(H³), 4.79 d (H⁴), 3.03 d (H⁵), 2.95 d (H²), 3.54 m and 1.68 m (THF),2.21 s and 2.06 s (tetramethylenediamine); I₁₂ =16.3 Hz, I₁₃ =5.4 Hz,I₄₅ =4.2 Hz. ##STR60## In order to record the ¹³ C-NMR-spectrum, the rawproduct is recrystalized from THF (crystalization at -78° C.). The ¹³C-NMR-spectrum of 14 (100 MHz; 10% in d₈ -THF, at 25° C.): δ(ppm)=84.6 t(C⁵), 97.6 (wide) (C¹), 100.4 d (C³), 153.9 d (C²), 187.7 (wide) (C⁴).The widening of the signals of the ¹³ C¹ and ¹³ C⁴ nuclei indicates thepresence of two Li-C bonds. In the reaction of 1.07 g of 14 withtrimethylchlorosilane, as described in Example 1, one obtains, afterprocessing or distillation, 0.85 g of a fraction of B.P. 45°-47° C./10⁻⁴torr, which, according to the ¹ H-NMR-spectrum, is a mixture of thethree stereoisomeric 1,4,5-tris (trimethylsilyl)-1,3-pentadienes (21)(65%), (22), (33%), and (23) (2%). ##STR61## It was shown in a parallelexperiment that in the reaction of pentadiene-1,4 with lithium, underthe same conditions of reaction but in the absence of the catalyst, theformation of 14 occurs at best in trace quantities only.

EXAMPLE 40 ##STR62## A solution of 0.34 g (1.1 mMoles) of2,5-diphenyl-1,6,6a-trithiapentalene 24 and 0.30 g (2.2 mMoles) of ZnCl₂(anhydrous) in 50 ml of absolute THF, is saturated at 0° C. withethylene (1 bar); immediately thereafter the preparation is mixed in anethylene atmosphere at 0° C. and under stirring, with 1.45 g (0.21Moles) of lithium sand. After a slight rise in temperature, ethyleneabsorption starts after 10-15 minutes, the rate of absorption beingmeasured with the aid of a gas burette attached to the reaction vessel.During the ethylene absorption, the suspension is vigorously stirred andthe temperature is kept at 0° C. Up to the end of the reaction, thereaction mixture absorbs within 6 hours 2.28 liters of ethylene (1 bar,20° C.). The suspension is filtered to separate the lithium hydride, andthe lithium hydride is washed with THF. Of the total of 81.0 ml of thefiltrate, 50 ml yield after evaporation of the THF, upon hydrolysis, 126ml of gas (at 20° C., 1 bar), which, according to MS analysis consistsof 84.8 Mole% of ethylene. On the basis of the amount of ethyleneobtained during hydrolysis, the vinyllithium yield is calculatedaccording to Equ. 7 at 76% (referred to ethylene). EXAMPLE 41

A solution of 1.61 g (5.2 mMoles) of2,5-diphenyl-1,6,6a-trithiapentalene (24) and 1.21 g (8.9 mMoles) ofZnCl₂ (anhydrous) in 100 ml of absolute THF is saturated at 0° C. withpropene (1 bar); immediately thereafter the preparation is mixed in apropene atmosphere at 0° C. and under stirring with 5.47 g (0.79 Moles)of lithium sand. The further performance of the experiment followedExample 40 as described for ethylene. Up to the end of the reaction, thereaction mixture absorbed within 12 hours 7.9 liters of propene (at 20°C., 1 bar). The suspension was filtered and the lithium hydride washedwith THF. Of the total of 167.0 ml of filtrate, 7.0 ml yielded uponhydrolysis 372 ml of gas (20° C., 1 bar), consisting of 88.8 Mole% ofpropene(balance: THF, H₂). From the amount of propene obtained uponhydrolysis, the yield of organolithium compounds LiC₃ H₅ was calculatedaccording to Equ. 8 at 99.7% (referred to propene). The mixing of 40 mlof the filtrate with trimethylchlorosilane, and the subsequentprocessing and distillation, as described in Example 1, yielded 11.9 gof the isomeric silanes (CH₃)₃ SiC₃ H₅, with the composition:trans-1-propenyltrimethylsilane, 80.0%; cis-1-propenyl-trimethylsilane,0.4%; isopropenyltrimethylsilane, 15.0%; and allyltrimethylsilane, 4.6%.The isolation of the organolithium compounds LiC₃ H₅ from the THFsolution, as described in Example 1, yields a product that consists of91.3% trans-propenyllithium.

EXAMPLE 42

To a solution of 25.1 g (0.22 Mole) of 1-octene and 1.23 g (4.0 mMoles)of 2,5-diphenyl-1,6,6a-trithiapentalene (24) in 100 ml of absolute THF,there are added consecutively at 0° C. and under stirring, 1.15 g (8.5mMoles) of ZnCl₂ (anhydrous) and, in small portions, 3.09 g (0.45 Moles)of lithium sand. The preparation was stirred for a total of 22 hours at0° C. During this period, 2.5-ml samples were withdrawn from thesolution, filtered, and the lithium content in the filtrates determinedacidimetrically. After 3.5, 6, and 22 hours, the lithium content in thesamples is 4.2, 4.6 and 5.4 mMoles, respectively, corresponding to alithium conversion to lithium octenyl and lithium hydride, according toEqu. 9, of 75, 83 and 97%. The preparation is filtered and the lithiumhydride is washed with THF. Of the total of 167.0 ml of the filtrate,47.0 ml are mixed, as described in Example 1, with 11.0 g (0.10 Moles)of trimethylchlorosilane. The processing or distillation yields 6.13 gof a fraction of B.P. 35°-43° C./0.2 torr, which, according to GCanalysis or BC-MS-coupling analysis and ¹ H-NMR-spectrum, consists of96.6% of trans-1-trimethylsilyl-1-octene (25). According to this result,##STR63## 1-octene is lithiated according to the method described with aselectivity greater than 96% in the trans-1 position.

Herein and in the claims, the catalyst is defined in the mannerconventionally used in the art, i.e., in terms of its components, ratherthan attempting to speculate on the nature or structure of an activematerial which may be formed from these components.

What is claimed is:
 1. A process for the preparation of organolithiumcompounds and lithium hydride comprising reacting lithium with anα-olefin or an α, w-diolefin in the presence of a catalyst formed bycontacting hetero-compounds of the general formula ##STR64## in which Xis sulfur or oxygen; R¹, R², R³ and R⁴ represent hydrogen, alkyl of upto 20 carbon atoms, cycloalkyl, aralkyl or aryl groups and/or two ormore of such groups are closed into an aliphatic or aromatic ringsystem; or a polycyclic aromatic selected from the group consisting ofanthracene, naphthalene, biphenyl with halides of transition metals fromgroup I_(b), II_(b), IV_(b) -VII_(b) and VIII of the periodic system. 2.The process of claim 1 wherein the catalyst is formed in situ during thereacting of lithium with an α-olefin or α,w-diolefin.
 3. The process ofclaim 1 wherein the catalyst is first formed and then introduced intothe presence of the lithium and the α-olefin or α,w-diolefin.
 4. Theprocess of claim 1 wherein cycloalkyl is selected from the groupconsisting of cyclopentyl, cyclohexyl and decahydronaphthyl; aralkyl isselected from the group consisting of benzyl, phenylethyl and naphthylmethyl; aryl is selected from the group consisting of phenyl, tolyl,xylyl, naphthyl, penanthryl and diphenyl.
 5. The process according toclaim 1, wherein the metal compound is of a metal selected from thegroup consisting of copper, gold, zinc, cadmium, titanium, zirconium,vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese,iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium,and platinum.
 6. The process according to claim 1, wherein the metalcompound is of a metal selected from the group consisting of copper,iron, zinc, palladium, platinum and rhodium.
 7. The process according toclaim 1, wherein the metal compound is selected from the groupconsisting of zinc chloride, iron (III) chloride, copper (I) chloride,copper (II) chloride, molybdenum (VI) chloride, titanium (IV) chloride,chromium (III) chloride, molybdenum (V) chloride, manganese (II)chloride, cobalt (II) chloride, nickel (II) chloride, nickel (II)acetylacetonate, rhodium (III) chloride, platinum (II) chloride, andpalladium (II) chloride.
 8. The catalyst according to claim 1, whereinthe metal compound is an anhydrous metal compound.
 9. The processaccording to claim 1, wherein a solvent is added to the lithium, to theα-olefin or the α,ω-diolefin and/or the catalyst.
 10. The processaccording to claim 9, wherein the solvent is a cyclic or an open-chainmonoether or polyether.
 11. The process according to claim 9, whereinthe solvent is tetrahydrofuran.
 12. The process according to claim 1,wherein the catalyst is formed in situ by contacting lithium withcompounds of the general formulae III, IV, V, VI or VII ##STR65## inwhich X is sulfur or oxygen.
 13. The process according to claim 12,wherein lithium is contacted with compounds of the general formulae III,IV, V, VI, or VII, and with a metal compound of transition metals fromgroup I_(b), II_(b), IV_(b), V_(b), VI_(b), VII_(b), and VIII of theperiodic system.
 14. The process according to claim 1, wherein lithiumis contacted with a catalyst consisting of isolated adducts fromcompounds III to VII and metal compounds of transition metals from groupI_(b), II_(b), IV_(b), V_(b), VI_(b), VII_(b), and VIII of the periodicsystem.
 15. The process according to claim 1, wherein the contactingtemperature is from about -100° C. to +100° C.
 16. The process accordingto claim 15, wherein the contacting temperature is from about -20° C. to+50° C.
 17. The process according to claim 1, wherein α-olefins of thegeneral formula CH₂ ═CHR are employed, in which R is H, alkyl, aryl,cycloalkyl or aralkyl.
 18. The process according to claim 1, whereinα,ω-diolefins of the formula CH₂ ═CH--(CHR)_(n) --CH═CH₂ are employed,in which R is hydrogen, alkyl, aryl, cycloalkyl or aralkyl and and n isan integer from 1 to
 6. 19. The process according to claim 14, wherein amember of the group consisting of the reaction products of the formula##STR66## are contacted with lithium.